Characterization of the continuous transition from atomic to molecular shape in the three-body Coulomb system

Abstract

We present an alternative, univocal characterization of the continuous transition from atomic to molecular shape in the Coulomb system constituted by two identical particles and a third particle with the opposite charge, as the mass ratio of the particles varies. Applying a marginal-conditional exact factorization to a variationally optimized wavefunction, we construct a nonadiabatic potential energy surface for the relative motion between the single particle and each of the identical particles. The transition is revealed through the evolution with the mass ratio of the topography of such surface and of the shapes of the associated marginal and conditional distributions. Our approach unifies and extends to the nonadiabatic regime the Born-Oppenheimer and charge-distribution pictures of molecular shape.